Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C231/00—Preparation of carboxylic acid amides
  • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
  • C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
  • C07C235/72—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms
  • C07C235/76—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
  • C07C235/78—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
  • C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
  • C07C249/12—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reactions not involving the formation of oxyimino groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
  • C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
  • C07C251/32—Oximes
  • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
  • C07C251/48—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring

Definitions

• the present application relates to several new processes for producing 2-
• N-methylacetamide (C) is obtained if 2- (2-hydroxyphenyl) -2- (methoxyimino) methyl acetate (A) or l-benzofuran-2,3-dione-3- (O-methyloxime) (B), reacted with methylamine (see, for example, EP-A 398692 or WO 95-24396):
• R represents substituted or unsubstituted alkyl
• R has the meaning given above, and X represents halogen, -O-CO-OR, -O-SO 2 -R 1 , or -O-SO 2 -OR, where R has the meaning given above, and R 1 represents alkyl or phenyl optionally substituted by alkyl .
• the saturated hydrocarbon chains such as alkyl are each straight-chain or branched.
• alkyl is C1-C4-alkyl, preferably methyl, ethyl, n- or i-propyl, n-, s- or i-butyl, n-pentyl or i-pentyl, in particular methyl, ethyl or n-propyl ,
• Halogen is preferred as the substituent for alkyl.
• Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
• Aryl stands for aromatic, mono- or polycyclic hydrocarbon rings, such as phenyl, naphthyl, anthranyl, phenanthryl, preferably phenyl or naphthyl, especially phenyl.
• Alkyl or halogen are suitable as substituents for aryl.
• R stands in particular for methyl, ethyl, fluoromethyl and difluoromethyl.
• R particularly preferably represents methyl
• R 1 particularly preferably represents methyl or tolyl.
• radical definitions given for these radicals in the respective combinations or preferred combinations of radicals are independently replaced by radical definitions of other preferred ranges, irrespective of the respectively specified combination of the radicals.
• the compounds according to the invention can optionally be in the form of mixtures of various possible isomeric forms, in particular stereoisomers, such as e.g. E- and Z-. Both the E and the Z isomers and any mixtures of these isomers are claimed.
• the method a) according to the invention has a number of advantages. So 2- (2-hydroxyphenyl) -2- (alkoxyimino) -N-methylacetamide derivatives of the formula
• the method b) according to the invention has a number of advantages.
• 2- (2-hydroxyphenyl) -2- (alkoxyimino) -N-methylacetamide derivatives of the formula (I) can be obtained in high yields and purities from easily accessible starting materials under technically completely unproblematic conditions.
• the method c) according to the invention has a number of advantages.
• 2- (2-hydroxyphenyl) -2- (alkoxyimino) -N-methylacetamide derivatives of the formula (I) can be obtained in high yields and purities from easily accessible starting materials under technically completely unproblematic conditions.
• the 2- (2-hydroxyphenyl) -2- (hydroxyimino) -N-methylacetamide of the formula (II) required as starting material for carrying out the process a) according to the invention is not yet known and is also a subject of the present application as a new chemical compound.
• 2- (2-Hydroxyphenyl) -2- (hydroxyimino) -N-methylacetamide of the formula (II) is obtained if
• the method d) according to the invention has a number of advantages. So you can
• the method e) according to the invention has a number of advantages.
• 2- (2-hydroxyphenyl) -2- (hydroxyimino) -N-methylacetamide of the formula (II) can be used in high
• A represents alkyl or optionally substituted aryl
• Formula (VII) provides a general definition of the (2-hydroxyphenyl) oxoacetic acid alkyl esters required as starting materials for carrying out process f) according to the invention.
• A represents alkyl or optionally substituted aryl, preferably methyl, ethyl, n- or i-propyl, n-, s- or i-butyl, n-pentyl, i-pentyl or substituted phenyl, where the substituents are preferably selected from the following list: fluorine, chlorine, bromine,
• the (2-hydroxyphenyl) oxoacetic acid alkyl esters of the general formula (VII) are known and can be prepared by known methods (compare, for example, J. Chem. Soc, Chem. Commun. (1972), (11), 668).
• the 2- (2-hydroxyphenyl) -2-N-methylacetamide of the formula (VI) required as starting material for carrying out the processes c) and e) according to the invention is not yet known and is also a subject of the present application as a new chemical compound.
• the (2-hydroxyphenyl) oxoacetic acid alkyl esters of the general formula (VII) are known and can be prepared by known methods (compare, for example, J. Chem. Soc, Chem. Commun. (1972), (11), 668).
• alkylating agents of the formula (III) which are also required as starting materials for carrying out the process a) according to the invention, all chemical compounds which can transfer alkyl groups are suitable. Chloromethane, bromomethane, iodomethane, dimethyl sulfate and dimethyl carbonate are preferred. Dimethyl sulfate and chloromethane are particularly preferred.
• alkoxyamines of the formula (V) or their acid addition combination required as starting materials for carrying out the processes b) and c) according to the invention plexes are commercially available synthetic chemicals.
• Preferred acid addition complexes are the hydrochlorides, hydrogen sulfates or sulfates.
• the hydroxylamine, or its acid addition complexes which is also required as the starting material for carrying out process d) and e) according to the invention, or its acid addition complexes, are commercially available synthetic chemicals.
• Preferred acid addition complexes are the hydrochlorides, hydrogen sulfates or sulfates.
• the methylamine which is furthermore required as starting material for carrying out processes f), g), h) and i) according to the invention is a commercially available synthetic chemical. It can be used both as a gas and as an alcoholic or aqueous solution.
• the 1-benzofuran-2,3-dione which is furthermore required as starting material for carrying out processes g) and i) according to the invention is known (cf. K. Fries, W.
• Suitable diluents for carrying out process a) according to the invention are all inert organic solvents. These include, by way of example and by way of preference, aliphatic, alicyclic or aromatic hydrocarbons, such as, for example, petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as, for example, diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane
• Process a) according to the invention is optionally carried out in the presence of a suitable acid acceptor.
• a suitable acid acceptor All conventional inorganic or organic bases are suitable as such. These include, for example and preferably, alkaline earth metal or alkali metal hydroxides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, sodium carbonate, potassium carbonate , Potassium hydrogen carbonate or sodium hydrogen carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N -Dimethylaminopyridine, diazabicyclooctane (DABCO), diaza
• Process a) according to the invention is optionally carried out in the presence of a suitable phase transfer catalyst.
• suitable phase transfer catalyst include, by way of example and by way of preference, quaternary ammonium salts, such as, for example, tetrabutylammonium bromide, chloride, hydrogen sulfate or sulfate, methyl trioctylammonium bromide or chloride, hydrogen sulfate or sulfate or 4-dimethylamino-N- (2-ethylhexyl) - pyridinium bromide or chloride, hydrogen sulfate or sulfate, quaternary phosphonium salts, such as, for example, tributyl-tetradecyl-phosphonium bromide or chloride, tetraphenylphosphonium bromide or chloride, crown ethers, such as, for example, dibenzo-18-crown-6, guanidinium alkyl salts
• reaction temperatures can be varied within a substantial range when carrying out process a) according to the invention. In general, temperatures from -80 ° C to 100 ° C, preferably at temperatures from 0 ° C to 60 ° C.
• Process a) according to the invention is generally carried out under normal pressure. However, it is also possible, under increased or reduced pressure - im
• 1 to 15 are generally employed per mole of 2- (2-hydroxyphenyl) -2- (hydroxyimino) -N-methylacetamide of the formula (II) Mol, preferably 1 to 4 mol of alkylating agent of formula (III).
• the procedure for a) according to the invention is generally carried out as follows.
• the 2- (2-hydroxyphenyl) -2- (hydroxyimino) -N-methylacetamide of the formula (II) is preferably in the presence of a diluent with a
• phase transfer catalyst for this, the alkylating agent of the formula (III) is added and the mixture is stirred, if appropriate at elevated temperature, until the reaction is complete. After the reaction is worked up in the usual manner. For example, volatile solvent fractions are distilled off and water is added, the product crystallizing.
• Suitable diluents for carrying out processes b), c), d) and e) are all inert organic solvents. These include, for example and preferably, ethers such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,
• 1,2-diethoxyethane or anisole Nitriles, such as acetonitrile, propionitrile, n- or i- Butyronitrile or benzonitrile; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric acid triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide; Sulfones such as sulfolane; Alcohols, such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol,
• Methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, preferred diluents are alcohols, their mixtures with water or pure water.
• Processes b), c), d) and e) according to the invention are optionally carried out in the presence of a buffer medium.
• All customary acid / salt mixtures which buffer the pH in the range from 1 to 7 can be used as buffer media.
• the mixture is preferably acetic acid / sodium acetate or no buffer medium.
• reaction temperatures can be carried out when the inventive compounds
• Processes b), c), d) and e) can be varied over a wide range. In general, temperatures from -20 ° C to 150 ° C, preferably at temperatures from 0 ° C to 80 ° C.
• Normal pressure carried out. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar.
• N-methylacetamides of formula (IV) generally 1 to 15 moles, preferably 1 to 4 moles of alkoxyamine of formula (V) or an acid addition complex thereof.
• the procedure is generally as follows.
• the 2- (2-hydroxyphenyl) -2- (methylimino) -N-methylacetamide of the formula (IV) or the 2- (2-hydroxyphenyl) -2- (oxo) -N-methylacetamide of the formula (VI) is preferred in the presence of a diluent with alkoxyamine or its acid addition complex, and optionally the buffer medium, and heated. After the reaction is worked up in the usual manner. For example, volatile solvent fractions are distilled off and mixed with
• the 2- (2-hydroxyphenyl) -2- (methylimino) -N-methylacetamide of the formula (IV) or the 2- (2-hydroxyphenyl-2- (oxo) -N-methylacetamide of the formula (VI) is preferably in In the presence of a diluent, hydroxylamine, or its acid addition complex, and, if appropriate, the buffer medium are added and heated, and the reaction is worked up in a conventional manner, for example by distilling off volatile solvent fractions and adding water, the product crystallizing.
• Suitable diluents for carrying out processes f), g), h) and i) are all inert organic solvents.
• alicyclic or aromatic hydrocarbons such as, for example, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, or trichloroethane; Ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones, such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Sulfox
• reaction temperatures can be varied within a substantial range when carrying out processes f), g), h) and i). In general, temperatures from -60 ° C to 100 ° C, preferably at temperatures from 0 ° C to 80 ° C.
• the processes f), g), h) and i) according to the invention are generally carried out under normal pressure. However, it is also possible to work under increased or reduced pressure - generally between 0.1 bar and 10 bar.
• Carboxylic acids especially dilute mineral acids or acetic acid, are used.
• Hydroxyphenyl) -2-oxo-N-methylacetamide of the formula (VI) is generally employed per mole of the compounds of the formula (VII) from 2 to 30 mol, preferably from 2 to 10 mol, of methylamine.
• Hydroxyphenyl) -2-oxo-N-methylacetamide of the formula (VI) is generally employed per mole of 1-benzofuran-2,3-dione of the formula (VIII) from 2 to 30 mol, preferably from 2 to 10 mol, of methylamine.
• the procedures f) and g) according to the invention are generally carried out as follows.
• the (2-hydroxyphenyl) -oxoacetic acid alkyl ester of the general formula (VII) or l-benzofuran-2,3-dione of the formula (VIII) is preferably mixed with gaseous methylamine or an aqueous or alcoholic solution thereof in the presence of a diluent.
• gaseous methylamine or an aqueous or alcoholic solution thereof in the presence of a diluent.
• After the reaction is worked up in the usual manner. For example, volatile constituents are distilled off or the product is filtered off and the product is obtained in high purity.
• the procedure h) and i) according to the invention is generally carried out as follows.
• the (2-hydroxyphenyl) -oxoacetic acid alkyl ester of the general formula (VII) or l-benzofuran-2,3-dione of the formula (VIII) is preferably mixed with gaseous methylamine or an aqueous or alcoholic solution thereof in the presence of a diluent.
• the reaction mixture is treated with acids and then worked up in the customary manner. For example, volatile constituents are distilled off and the product is obtained in high purity.
• 2- (2-hydroxyphenyl) -2- (alkoxyimino) -N-methylacetamide derivatives of the formula (I) can be used as intermediates for the preparation of fungicides (compare, for example, EP-A 398692).
• the compounds of the formula (II) or of the formulas (IV) and (VI) can be used as intermediates, in particular for the preparation of fungicides.
• Methylamine solution (18.6 mmol) was added and the mixture was stirred at room temperature for 30 min. 20 ml of saturated NaCl solution are added and the mixture is extracted three times with 25 ml of ethyl acetate each time. The combined organic phases are stirred for 15 min with 50 ml of 10% aqueous hydrochloric acid. The organic phase is dried and concentrated in vacuo to an oil (2.45 g).

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• 1999
  • 1999-11-26 DE DE19956920A patent/DE19956920A1/de not_active Withdrawn
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